以热点问题为导向的高分子物理综合实验设计

传统高分子物理实验教学存在知识陈旧、知识点分散、实验之间彼此独立等问题。本文以聚合物透明性和耐热性难兼顾这一问题为导向,以热点材料生物基可降解聚乳酸为研究对象,通过综合实验设计将高分子加工、结晶行为、宏观物理性能及表征方法串联起来。本文设计的实验课程可以促进学生对多学科相关知识的融会贯通,同时培养学生独立自主解决问题的能力,非常适用于高分子专业的实验教学。     

非绝热分子动力学模拟A位阳离子对钙钛矿热载流子弛豫的影响

钙钛矿具有优异的光学和电学性质,近年来成为太阳能电池领域的研究热点.大量实验报道钙钛矿热载流子弛豫时间变化顺序为CsPbBr₃>MAPbBr₃(MA=CH₃NH₃)>FAPbBr₃[FA=HC(NH₂)₂],但A位阳离子(Cs⁺,MA⁺,FA⁺)对弛豫快慢的影响机制仍不明确.采用基于含时密度泛函理论的非绝热动力学方法研究了上述3种钙钛矿热电子和热空穴的能量弛豫动力学,计算得到的热载流子弛豫时间与实验结果吻合.结果表明,A位阳离子通过静电和氢键作用影响其与无机Pb—Br骨架的电子-振动耦合,使非绝热耦合强度遵从FAPbBr₃>MAPbBr₃>CsPbBr₃的变化趋势,进而使热载流子弛豫时间尺度变化趋势与之相同,表明合理选择A位阳离子可以优化钙钛矿太阳能电池的性能.     

石墨烯膜质子传输巨大光效应的微观机理

Graphene monolayers are permeable to thermal protons and impermeable to other atoms and molecules, exhibiting their potential applications in fuel cell technologies and hydrogen isotope separation. Furthermore, the giant photoeffect in proton transport through catalytically activated graphene membranes was reported by Geim et al. Their experiment showed that the synergy between illumination and the catalytically active metal plays a key role in this photoeffect. Geim et al. suggested that the local photovoltage created between metal nanoparticles and graphene could funnel protons and electrons toward the metal nanoparticles for the production of hydrogen, while repelling holes away from them, causing the giant photoeffect. However, based on static electric field theory, this explanation is not convincing and the work lacks an analysis on the microscopic mechanism of this effect. Herein, we provide the exact microscopic mechanism behind this phenomenon. In semi-metal pristine graphene, most photon excited hot electrons relax to lower energy states within a timescale of 10⁻¹² s, while the typical timescale of a chemical reaction is 10⁻⁶ s. Thus, hot electrons excited by incident photons relax to lower energy states before reacting with protons through the graphene. When graphene is decorated with metal, electron transfer between the graphene and the metal, induced by different work functions, would result in the formation of interface dipoles. When using metals such as Pt, Pd, Ni, etc., which can strongly interact with graphene, local dipoles form. Protons are trapped around the negative poles of the local dipoles, while electrons are around the positive poles. Upon illumination, the electrons are excited to metastable excited states with higher energy levels. Due to the energy barriers around them, the free electrons in the metastable excited states will have a relatively longer lifetime, which facilitates the production of hydrogen through their effective reaction with protons that permeated through the graphene. The concentration of high-energy electrons under illumination was estimated, and the results showed that more electrons are energized to the excited state with strong illumination. According to the analysis, the giant photoeffect in proton transport through the catalytically activated graphene membrane is attributed to long-lived hot electrons and a fast proton transport rate. Since there is no change in the activation energy of the reaction, the metal catalyst increases the rate of the reaction by increasing the number of successful collisions between the reactants to produce the significant photoeffect. This might lead to a new microscopic mechanism that clarifies the role of the catalyst in improving the efficiency of photo(electro)catalytic reactions.     

CFETR产氚包层与偏滤器部件在热室内维修与退役流程的概念设计

为保证聚变堆环境的核安全,需要在热室内及时对产氚包层及偏滤器进行检测、维修或退役处理。针对 CFETR 产氚包层与偏滤器结构特点,设计了一套在热室内维修与退役处理的工作流程,包括放射性废物处理、核去污、除氚等关键工艺,并参照 ITER 设计,遵循 ALARA 原则,完成了热室内各功能区域的放射性分级。     

低活化马氏体钢热等静压焊接接头性能初步研究

研究了低活化马氏体钢(CLF-1)热等静压(HIP)焊接接头的性能,经980℃/1h/空冷+740℃/2h/空冷的性能热处理后,接头组织保持着CLF-1钢母材回火马氏体组织;常温拉伸性能与母材相当,断口为韧窝状且有第二相粒子产生,为塑性断裂且断于焊缝;常温冲击功最高为母材的26.2%。初步分析认为焊接表面制备状态、表面污染物、表面清洗状态、表面氧化膜都会影响基体原子充分扩散,导致界面扩散层不均匀,焊缝裂纹敏感性增强,冲击功低,且不稳定。     

电场引发的嵌有碳纳米管的黑索金复合材料分解模拟

以电场作为引燃条件对含能材料的分解过程进行了研究。利用黑索金(RDX)单晶结构,构建了镶嵌有碳纳米管(CNT)的黑索金(RDX)复合结构模型,利用反应分子动力学模拟研究了该材料在外电场下的响应。结果表明构建的复合结构在方向沿CNT 的匀强电场下,能够以CNT 为中心形成反应热点;随着热点的成长,形成了自发行进的燃烧层,可以分解掉整个体系。     

热拉伸的超高分子量聚乙烯的晶体结构和力学性能

讨论了超高分子量聚乙烯（ＵＨＭＷ－ＰＥ）的熔融一次拉伸和二次拉伸的晶体结构和力学性能．利用ＷＡＸＤ和ＳＡＸＤ测定了拉伸片的晶体取向因子和极图,晶粒尺寸,晶体畸变,长周期等晶体结构．用ＤＳＣ和ＶＥＳ测定热性能和动态力学性能．应力－应变实验测定拉伸片的杨氏模量,断裂强度和伸长．这些实验结果说明ＵＨＭＷ－ＰＥ经二次拉伸能产生正交晶系的伸直链晶体．二次拉伸片由折叠链片晶和伸直链晶体两元结构组成．二次拉伸片的杨氏模量比一次拉伸片有大幅度提高．二次拉伸片的晶体结构和力学性能是在一次拉伸的基础上形成的．     

真空硅热还原氧化锌的热力学分析

通过热力学计算并分析了真空硅热法还原氧化锌反应的吉布斯自由能. 结果表明, 在1100-1500 K温度范围内硅热还原氧化锌具有热力学上的可行性, 但是生成的SiO₂与反应物ZnO反应生成炉渣2ZnO·SiO₂, 导致约50% (w)的ZnO不能被还原. 如果加入CaO与SiO₂造渣, 就能抑制2ZnO·SiO₂的生成, 保证ZnO完全被还原成金属锌. 热力学计算表明, 造渣反应和真空工艺都可以降低还原反应的吉布斯自由能. 实验结果表明, 热镀锌灰中分离出的ZnO在温度为1448 K、真空度为20 Pa、反应时间为2 h的条件下通过硅热还原可得到具有良好结晶形貌的金属锌, 还原率为92.81%. 经X射线衍射(XRD)分析, 反应后的残渣主要成分为2CaO·SiO₂.